Plurality of host materials and organic electroluminescent device comprising the same

ABSTRACT

The present disclosure relates to a plurality of host materials comprising a first host material comprising a compound represented by formula 1, and a second host material comprising a compound represented by formula 2, and an organic electroluminescent device comprising the same. By comprising a specific combination of compounds of the present disclosure as host materials, it is possible to provide an organic electroluminescent device having higher luminous efficiency and/or longer lifetime properties as compared with a conventional organic electroluminescent device.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Pat. Application No.17/075,581, filed Oct. 20, 2020, which claims the benefit of KR10-2019-0132762, filed Oct. 24, 2019, each of which is incorporated byreference herein in its entirety.

TECHNICAL FIELD

The present disclosure relates to a plurality of host materials and anorganic electroluminescent device comprising the same.

BACKGROUND ART

In 1987, Tang et al. of Eastman Kodak first developed a small moleculegreen organic electroluminescent device (OLED) of TPD/Alq3 bilayerconsisting of a light-emitting layer and a charge transport layer. Sincethen, the research on an OLED has been rapidly carried out, and it hasbeen commercialized. At present, phosphorescent materials, which provideexcellent luminous efficiency in realizing panels, are mainly used inorganic electroluminescent devices. Thus, an OLED which has highluminous efficiency and/or long lifetime is required for long time usesand high resolution of displays.

Korean Patent Appl. Laid-Open Nos. 2015-0086721, 2014-0096203, and2015-0116776 disclose a plurality of host materials using carbazolederivative compounds. However, the aforementioned references do notspecifically disclose a plurality of host materials described in thepresent disclosure. Further, there is a need for the development of alight-emitting material having improved performances, for example,improved luminous efficiency and/or lifetime properties as compared withthe host materials disclosed in the aforementioned references.

DISCLOSURE OF INVENTION Technical Problem

The objective of the present disclosure is to provide an organicelectroluminescent device having higher luminous efficiency and/orlonger lifetime properties, by comprising a specific combination ofcompounds as host materials.

Solution to Problem

The present inventors found that the above objective can be achieved bya plurality of host materials comprising a first host materialcomprising a compound represented by the following formula 1, and asecond host material comprising a compound represented by the followingformula 2:

wherein,

-   ring A, ring B, and ring C, each independently, represent a    substituted or unsubstituted benzene ring, or a substituted or    unsubstituted naphthalene ring;

-   Y represents O, S, or NRa;

-   Ra represents —L₂—Ar₂;

-   Ar₁ and Ar₂, each independently, represent a substituted or    unsubstituted (C6-C30)aryl; a substituted or unsubstituted (3- to    30-membered)heteroaryl containing at least one of nitrogen(s),    oxygen(s), and sulfur(s); or a substituted or unsubstituted    di(C6-C30)arylamino;

-   L₁ and L₂, each independently, represent a single bond, a    substituted or unsubstituted (C6-C30)arylene, or a substituted or    unsubstituted (3- to 30-membered)heteroarylene; and

-   n represents an integer of 0 or 1, with the proviso that if n is 0,    both ring A and ring B are a substituted or unsubstituted    naphthalene ring;

-   

-   wherein,    -   HAr represents a substituted or unsubstituted        nitrogen-containing (3- to 30-membered)heteroaryl;    -   L₃ represents a naphthylene unsubstituted or substituted with        deuterium(s), a biphenylene unsubstituted or substituted with        deuterium(s), a terphenylene unsubstituted or substituted with        deuterium(s), or a -phenylene-naphthylene- unsubstituted or        substituted with deuterium(s); and    -   R₁ to R₈, each independently, represent hydrogen, deuterium, or        a (C6-C30)aryl unsubstituted or substituted with at least one of        deuterium(s) and a (C6-C30)aryl(s).

Advantageous Effects of Invention

By comprising a specific combination of compounds of the presentdisclosure as host materials, it is possible to provide an organicelectroluminescent device having higher luminous efficiency and/orlonger lifetime properties as compared with the conventional organicelectroluminescent device, and manufacture a display system or a lightsystem using the same.

MODE FOR THE INVENTION

Hereinafter, the present disclosure will be described in detail.However, the following description is intended to explain thedisclosure, and is not meant in any way to restrict the scope of thedisclosure.

The term “organic electroluminescent material” in the present disclosuremeans a material that may be used in an organic electroluminescentdevice, and may comprise at least one compound. The organicelectroluminescent material may be comprised in any layer constitutingan organic electroluminescent device, as necessary. For example, theorganic electroluminescent material may be a hole injection material, ahole transport material, a hole auxiliary material, a light-emittingauxiliary material, an electron blocking material, a light-emittingmaterial (containing host and dopant materials), an electron buffermaterial, a hole blocking material, an electron transport material, anelectron injection material, etc.

The term “a plurality of organic electroluminescent materials” in thepresent disclosure means an organic electroluminescent material(s)comprising a combination of at least two compounds, which may becomprised in any layer constituting an organic electroluminescentdevice. It may mean both a material before being comprised in an organicelectroluminescent device (for example, before vapor deposition) and amaterial after being comprised in an organic electroluminescent device(for example, after vapor deposition). For example, a plurality oforganic electroluminescent materials may be a combination of at leasttwo compounds which may be comprised in at least one of a hole injectionlayer, a hole transport layer, a hole auxiliary layer, a light-emittingauxiliary layer, an electron blocking layer, a light-emitting layer, anelectron buffer layer, a hole blocking layer, an electron transportlayer, and an electron injection layer. At least two compounds may becomprised in the same layer or different layers, and may bemixture-evaporated or co-evaporated, or may be individually evaporated.

The term “a plurality of host materials” in the present disclosure meansan organic electroluminescent material comprising a combination of atleast two host materials. It may mean both a material before beingcomprised in an organic electroluminescent device (for example, beforevapor deposition) and a material after being comprised in an organicelectroluminescent device (for example, after vapor deposition). Theplurality of host materials of the present disclosure may be comprisedin any light-emitting layer constituting an organic electroluminescentdevice. The two or more compounds comprised in the plurality of hostmaterials of the present disclosure may be included in onelight-emitting layer or may be respectively included in differentlight-emitting layers. For example, the two or more host materials maybe mixture-evaporated to form a layer, or separately co-evaporated atthe same time to form a layer.

Herein, the term “(C6-C30)aryl” or “(C6-C30)arylene” is meant to be amonocyclic or fused ring radical derived from an aromatic hydrocarbonhaving 6 to 30 ring backbone carbon atoms. The number of ring backbonecarbon atoms is preferably 6 to 20, and more preferably 6 to 15. Theabove aryl or arylene may be partially saturated, and may comprise aspiro structure. The above aryl may include phenyl, biphenyl, terphenyl,naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl,phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl,phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl,tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl,spirobifluorenyl, spiro[fluorene-benzofluorene]yl, azulenyl, etc. Morespecifically, the aryl may include phenyl, 1-naphthyl, 2-naphthyl,1-anthryl, 2-anthryl, 9-anthryl, benzanthryl, 1-phenanthryl,2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl,naphthacenyl, pyrenyl, 1-chrysenyl, 2-chrysenyl, 3-chrysenyl,4-chrysenyl, 5-chrysenyl, 6-chrysenyl, benzo[c]phenanthryl,benzo[g]chrysenyl, 1-triphenylenyl, 2-triphenylenyl, 3-triphenylenyl,4-triphenylenyl, 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl,9-fluorenyl, benzofluorenyl, dibenzofluorenyl, 2-biphenylyl,3-biphenylyl, 4-biphenylyl, o-terphenyl, m-terphenyl-4-yl,m-terphenyl-3-yl, m-terphenyl-2-yl, p-terphenyl-4-yl, p-terphenyl-3-yl,p-terphenyl-2-yl, m-quaterphenyl, 3-fluoranthenyl, 4-fluoranthenyl,8-fluoranthenyl, 9-fluoranthenyl, benzofluoranthenyl, o-tolyl, m-tolyl,p-tolyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesityl, o-cumenyl, m-cumenyl,p-cumenyl, p-tert-butylphenyl, p-(2-phenylpropyl)phenyl,4′-methylbiphenylyl, 4″-tert-butyl-p-terphenyl-4-yl,9,9-dimethyl-1-fluorenyl, 9,9-dimethyl-2-fluorenyl,9,9-dimethyl-3-fluorenyl, 9,9-dimethyl-4-fluorenyl,9,9-diphenyl-1-fluorenyl, 9,9-diphenyl-2-fluorenyl,9,9-diphenyl-3-fluorenyl, 9,9-diphenyl-4-fluorenyl, etc.

The term “(3- to 50-membered)heteroaryl” or “(3- to30-membered)heteroarylene” is an aryl or an arylene having 3 to 50 or 3to 30 ring backbone atoms, in which the number of ring backbone atoms ispreferably 3 to 30, more preferably 5 to 20, and including at least one,preferably 1 to 4 heteroatoms selected from the group consisting of B,N, O, S, Si, and P. The above heteroaryl(ene) may be a monocyclic ring,or a fused ring condensed with at least one benzene ring; may bepartially saturated; may be one formed by linking at least oneheteroaryl or aryl group to a heteroaryl group via a single bond(s); andmay comprise a spiro structure. The above heteroaryl may include amonocyclic ring-type heteroaryl such as furyl, thiophenyl, pyrrolyl,imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl,isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl,tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl,etc., and a fused ring-type heteroaryl such as benzofuranyl,benzothiophenyl, isobenzofuranyl, dibenzofuranyl, benzonaphthofuranyl,dibenzothiophenyl, benzonaphthothiophenyl, benzimidazolyl,benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl,isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl,isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, naphthyridinyl,carbazolyl, benzocarbazolyl, phenoxazinyl, phenanthridinyl,phenanthrooxazolyl, benzodioxolyl, etc. More specifically, theheteroaryl may include 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, pyrazinyl,2-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 6-pyrimidinyl,1,2,3-triazin-4-yl, 1,2,4-triazin-3-yl, 1,3,5-triazin-2-yl,1-imidazolyl, 2-imidazolyl, 1-pyrazolyl, 1-indolidinyl, 2-indolidinyl,3-indolidinyl, 5-indolidinyl, 6-indolidinyl, 7-indolidinyl,8-indolidinyl, 2-imidazopyridyl, 3-imidazopyridyl, 5-imidazopyridyl,6-imidazopyridyl, 7-imidazopyridyl, 8-imidazopyridyl, 3-pyridyl,4-pyridyl, 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl,6-indolyl, 7-indolyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl,4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 2-furyl,3-furyl, 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl,6-benzofuranyl, 7-benzofuranyl, 1-isobenzofuranyl, 3-isobenzofuranyl,4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl,7-isobenzofuranyl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl,6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl,4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl,8-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl,1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl, 9-carbazolyl,azacarbazolyl-1-yl, azacarbazolyl-2-yl, azacarbazolyl-3-yl,azacarbazolyl-4-yl, azacarbazolyl-5-yl, azacarbazolyl-6-yl,azacarbazolyl-7-yl, azacarbazolyl-8-yl, azacarbazolyl-9-yl,1-phenanthridinyl, 2-phenanthridinyl, 3-phenanthridinyl,4-phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl,8-phenanthridinyl, 9-phenanthridinyl, 10-phenanthridinyl, 1-acridinyl,2-acridinyl, 3-acridinyl, 4-acridinyl, 9-acridinyl, 2-oxazolyl,4-oxazolyl, 5-oxazolyl, 2-oxadiazolyl, 5-oxadiazolyl, 3-furazanyl,2-thienyl, 3-thienyl, 2-methylpyrrol-1-yl, 2-methylpyrrol-3-yl,2-methylpyrrol-4-yl, 2-methylpyrrol-5-yl, 3-methylpyrrol-1-yl,3-methylpyrrol-2-yl, 3-methylpyrrol-4-yl, 3-methylpyrrol-5-yl,2-tert-butylpyrrol-4-yl, 3-(2-phenylpropyl)pyrrol-1-yl,2-methyl-1-indolyl, 4-methyl-1-indolyl, 2-methyl-3-indolyl,4-methyl-3-indolyl, 2-tert-butyl-1-indolyl, 4-tert-butyl-1-indolyl,2-tert-butyl-3-indolyl, 4-tert-butyl-3-indolyl, 1-dibenzofuranyl,2-dibenzofuranyl, 3-dibenzofuranyl, 4-dibenzofuranyl,1-dibenzothiophenyl, 2-dibenzothiophenyl, 3-dibenzothiophenyl,4-dibenzothiophenyl, 1-silafluorenyl, 2-silafluorenyl, 3-silafluorenyl,4-silafluorenyl, 1-germafluorenyl, 2-germafluorenyl, 3-germafluorenyl,4-germafluorenyl, etc. “Halogen” includes F, Cl, Br, and I.

In addition, “ortho (o-),” “meta (m-),” and “para (p-)” are prefixes,which represent the relative positions of substituents, respectively.Ortho indicates that two substituents are adjacent to each other, andfor example, when two substituents in a benzene derivative occupypositions 1 and 2, it is called an ortho position. Meta indicates thattwo substituents are at positions 1 and 3, and for example, when twosubstituents in a benzene derivative occupy positions 1 and 3, it iscalled a meta position. Para indicates that two substituents are atpositions 1 and 4, and for example, when two substituents in a benzenederivative occupy positions 1 and 4, it is called a para position.

Herein, “substituted” in the expression “substituted or unsubstituted”means that a hydrogen atom in a certain functional group is replacedwith another atom or another functional group, i.e., a substituent. Inthe present disclosure, the substituents of the substituted benzene, thesubstituted naphthalene, the substituted aryl, the substituted arylene,the substituted heteroaryl, the substituted heteroarylene, thesubstituted alkyl, the substituted cycloalkyl, the substituted alkoxy,the substituted trialkylsilyl, the substituted dialkylarylsilyl, thesubstituted alkyldiarylsilyl, the substituted triarylsilyl, thesubstituted mono-or di- alkylamino, the substituted mono- or di-arylamino, and the substituted alkylarylamino, each independently, areat least one selected from the group consisting of deuterium; a halogen;a cyano; a carboxyl; a nitro; a hydroxyl; a (C1-C30)alkyl; ahalo(C1-C30)alkyl; a (C2-C30)alkenyl; a (C2-C30)alkynyl; a(C1-C30)alkoxy; a (C1-C30)alkylthio; a (C3-C30)cycloalkyl; a(C3-C30)cycloalkenyl; a (3- to 7-membered)heterocycloalkyl; a(C6-C30)aryloxy; a (C6-C30)arylthio; a (3- to 50-membered)heteroarylunsubstituted or substituted with at least one of a (C1-C30)alkyl(s), a(C6-C30)aryl(s), and a di(C6-C30)arylamino(s); a (C6-C30)arylunsubstituted or substituted with at least one of deuterium(s), acyano(s), a (C1-C30)alkyl(s), a (3- to 50-membered)heteroaryl(s), adi(C6-C30)arylamino(s), and a tri(C6-C30)arylsilyl(s); atri(C1-C30)alkylsilyl; a tri(C6-C30)arylsilyl; adi(C1-C30)alkyl(C6-C30)arylsilyl; a (C1-C30)alkyldi(C6-C30)arylsilyl; anamino; a mono- or di- (C1-C30)alkylamino; a mono- or di-(C6-C30)arylamino; a (C1-C30)alkyl(C6-C30)arylamino; a(C1-C30)alkylcarbonyl; a (C1-C30)alkoxycarbonyl; a (C6-C30)arylcarbonyl;a di(C6-C30)arylboronyl; a di(C1-C30)alkylboronyl; a(C1-C30)alkyl(C6-C30)arylboronyl; a (C6-C30)aryl(C1-C30)alkyl; and a(C1-C30)alkyl(C6-C30)aryl. Preferably, the substituents may be at leastone selected from the group consisting of deuterium; a (C1-C20)alkyl; a(C6-C25)aryl unsubstituted or substituted with at least one ofdeuterium(s), a (C1-C20)alkyl(s), a (3- to 30-membered)heteroaryl(s),and a di(C6-C25)arylamino(s); a (3- to 30-membered)heteroarylunsubstituted or substituted with at least one of a (C1-C20)alkyl(s) anda (C6-C25)aryl(s); and a di(C6-C20)arylamino. More preferably, thesubstituents may be at least one selected from the group consisting ofdeuterium; a (C1-C10)alkyl; and a (C6-C20)aryl unsubstituted orsubstituted with deuterium(s). For example, the substituents may be atleast one selected from the group consisting of deuterium; a methyl; aphenyl unsubstituted or substituted with deuterium(s); a naphthyl; abiphenyl; and a terphenyl.

In the formulas of the present disclosure, the heteroaryl, theheteroarylene, and the heterocycloalkyl, each independently, may containat least one heteroatom selected from B, N, O, S, Si, and P. Also, theheteroatom may be bonded to at least one selected from the groupconsisting of hydrogen, deuterium, a halogen, a cyano, a substituted orunsubstituted (C1-C30)alkyl, a substituted or unsubstituted(C6-C30)aryl, a substituted or unsubstituted (3-to30-membered)heteroaryl, a substituted or unsubstituted(C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, asubstituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted orunsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted orunsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted orunsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono-or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, and a substituted or unsubstituted(C1-C30)alkyl(C6-C30)arylamino.

In formula 1, ring A, ring B, and ring C, each independently, representa substituted or unsubstituted benzene ring, or a substituted orunsubstituted naphthalene ring. According to one embodiment of thepresent disclosure, ring A, ring B, and ring C, each independently, maybe an unsubstituted benzene ring or an unsubstituted naphthalene ring.

In formula 1, n represents an integer of 0 or 1; Y represents O, S, orNRa; and Ra represents —L₂—Ar₂. If n is 0, both ring A and ring Brepresent a substituted or unsubstituted naphthalene ring, preferably anunsubstituted naphthalene ring.

Ar₁ and Ar₂, each independently, represent a substituted orunsubstituted (C6-C30)aryl; a substituted or unsubstituted (3- to30-membered)heteroaryl containing at least one of nitrogen(s),oxygen(s), and sulfur(s); or a substituted or unsubstituteddi(C6-C30)arylamino. According to one embodiment of the presentdisclosure, Ar₁ and Ar₂, each independently, represent a substituted orunsubstituted (C6-C25)aryl; a substituted or unsubstituted (5- to25-membered)heteroaryl containing at least one of nitrogen(s),oxygen(s), and sulfur(s); or a substituted or unsubstituteddi(C6-C25)arylamino. According to another embodiment of the presentdisclosure, Ar₁ and Ar₂, each independently, represent a (C6-C25)arylunsubstituted or substituted with a (C1-C10)alkyl(s); a (5- to20-membered)heteroaryl unsubstituted or substituted with a(C6-C18)aryl(s) and containing at least one of nitrogen(s), oxygen(s),and sulfur(s); or a di(C6-C18)arylamino unsubstituted or substitutedwith a (C6-C18)aryl(s). Specifically, Ar₁ may be a substituted orunsubstituted phenyl, a substituted or unsubstituted naphthyl, asubstituted or unsubstituted biphenyl, a substituted or unsubstitutedterphenyl, a substituted or unsubstituted pyridyl, a substituted orunsubstituted pyrimidinyl, a substituted or unsubstitutedbenzofuropyrimidinyl, a substituted or unsubstituted triazinyl, asubstituted or unsubstituted quinolyl, a substituted or unsubstitutedquinazolinyl, a substituted or unsubstituted benzoquinazolinyl, asubstituted or unsubstituted quinoxalinyl, a substituted orunsubstituted benzoquinoxalinyl, a substituted or unsubstitutedcarbazolyl, a substituted or unsubstituted benzocarbazolyl, asubstituted or unsubstituted dibenzothiophenyl, a substituted orunsubstituted benzothiophenyl, a substituted or unsubstituteddibenzofuranyl, a substituted or unsubstituted benzofuranyl, asubstituted or unsubstituted naphthyridinyl, a substituted orunsubstituted fluorenyl, a substituted or unsubstituted benzofluorenyl,a substituted or unsubstituted spirobifluorenyl, a substituted orunsubstituted triphenylenyl, a substituted or unsubstitutedbenzonaphthofuranyl, a substituted or unsubstitutedbenzonaphthothiophenyl, a substituted or unsubstituted diphenylamino, asubstituted or unsubstituted naphthylphenylamino, or a substituted orunsubstituted biphenylphenylamino. For example, Ar₁ and Ar₂, eachindependently, may represent a phenyl; a naphthyl; a biphenyl; aterphenyl; a dimethylfluorenyl; a dimethylbenzofluorenyl; aspirobifluorenyl; a pyridyl substituted with a phenyl(s); a pyrimidinylsubstituted with a phenyl(s); a triazinyl substituted with a phenyl(s);a quinolyl substituted with a phenyl(s); a quinazolinyl substituted withat least one of a phenyl(s) and a naphthyl(s); a quinoxalinylsubstituted with at least one of a phenyl(s) and a naphthyl(s); anaphthyridinyl substituted with a phenyl(s); a dibenzothiophenyl; adibenzothiofuranyl; a carbazolyl substituted with a phenyl(s); abenzofuropyrimidinyl substituted with a phenyl(s); a benzoquinazolinylsubstituted with a phenyl(s); a benzoquinoxalinyl substituted with aphenyl(s); a benzocarbazolyl substituted with a phenyl(s); adiphenylamino; a phenylnaphthylamino; a phenylbiphenylamino; adiphenylamino substituted with a naphthyl(s); a phenylbiphenylaminosubstituted with a naphthyl(s), etc.

L₁ and L₂, each independently, represent a single bond, a substituted orunsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to30-membered)heteroarylene. According to one embodiment of the presentdisclosure, L₁ and L₂, each independently, represent a single bond, asubstituted or unsubstituted (C6-C25)arylene, or a substituted orunsubstituted (5- to 25-membered)heteroarylene. According to anotherembodiment of the present disclosure, L₁ and L₂, each independently,represent a single bond; an unsubstituted (C6-C18)arylene; or a (5- to20-membered)heteroarylene unsubstituted or substituted with a(C6-C18)aryl(s). For example, L₁ and L₂, each independently, mayrepresent a single bond; a phenylene; a naphthylene; a biphenylene; atriazinylene substituted with a phenyl(s); a pyrimidinylene substitutedwith a phenyl(s); a quinolylene; a quinazolinylene unsubstituted orsubstituted with a phenyl(s); a quinoxalinylene unsubstituted orsubstituted with a phenyl(s); a naphthyridinylene; abenzofuropyrimidinylene; a benzoquinazolinylene; a carbazolylene; abenzoquinoxalinylene; a benzocarbazolylene, etc.

The formula 1 may be represented by any one of the following formulas1-1 to 1-7.

In formulas 1-1 to 1-7, Ar₁, L₁, and Y are as defined in formula 1.

In formulas 1-1 to 1-7, R₁₁ to R₂₇, each independently, representhydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted(C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, asubstituted or unsubstituted (3- to 30-membered)heteroaryl, asubstituted or unsubstituted (C3-C30)cycloalkyl, a substituted orunsubstituted (C1-C30)alkoxy, a substituted or unsubstitutedtri(C1-C30)alkylsilyl, a substituted or unsubstituteddi(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted(C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstitutedtri(C6-C30)arylsilyl; a substituted or unsubstituted mono- ordi-(C1-C30)alkylamino; a substituted or unsubstituted mono- ordi-(C6-C30)arylamino, or a substituted or unsubstituted(C1-C30)alkyl(C6-C30)arylamino. For example, R₁₁ to R₂₇ may representhydrogen.

In formulas 1-1 to 1-7, a, d, h, m, q, and r, each independently,represent an integer of 1 to 6; and b, c, e, f, g, i, j, k, l, o, and p,each independently, represent an integer of 1 to 4, in which if a to mand o to r, each independently, are an integer of 2 or more, each ofR₁₁, each of R₁₂, each of R₁₃, each of R₁₄, each of R₁₅, each of R₁₆,each of R₁₇, each of R₁₈, each of R₁₉, each of R₂₀, each of R₂₁, each ofR₂₂, each of R₂₃, each of R₂₄, each of R₂₅, each of R₂₆, and each of R₂₇may be the same or different.

In formula 2, HAr represents a substituted or unsubstitutednitrogen-containing (3- to 30-membered)heteroaryl. According to oneembodiment of the present disclosure, HAr represents a substituted orunsubstituted (5- to 25-membered)heteroaryl containing at least onenitrogen. According to another embodiment of the present disclosure, HArrepresents a (5- to 20-membered)heteroaryl substituted with a(C6-C30)aryl(s) and containing at least one nitrogen. Specifically, HArmay represent a substituted or unsubstituted triazinyl, a substituted orunsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, asubstituted or unsubstituted quinazolinyl, a substituted orunsubstituted benzoquinazolinyl, a substituted or unsubstitutedquinoxalinyl, a substituted or unsubstituted benzoquinoxalinyl, asubstituted or unsubstituted quinolyl, a substituted or unsubstitutedbenzoquinolyl, a substituted or unsubstituted isoquinolyl, a substitutedor unsubstituted benzoisoquinolyl, a substituted or unsubstitutedtriazolyl, a substituted or unsubstituted pyrazolyl, a substituted orunsubstituted naphthyridinyl, or a substituted or unsubstitutedbenzothienopyrimidinyl. For example, HAr may represent a substitutedtriazinyl, in which the substituent of the substituted triazinyl may beat least one, preferably two selected from the group consisting of aphenyl(s); a phenyl(s) substituted with deuterium(s); a naphthyl(s); abiphenyl(s); and a terphenyl(s).

In formula 2, L₃ represents a naphthylene unsubstituted or substitutedwith deuterium(s), a biphenylene unsubstituted or substituted withdeuterium(s), a terphenylene unsubstituted or substituted withdeuterium(s), or a -phenylene-naphthylene- unsubstituted or substitutedwith deuterium(s). According to one embodiment of the presentdisclosure, L₃ represents a naphthylene unsubstituted or substitutedwith deuterium(s); an unsubstituted biphenylene; or an unsubstituted-phenylene-naphthylene-. The -phenylene-naphthylene- refers to that thephenylene therein may be bonded to HAr or the naphthylene therein may bebonded to HAr.

In formula 2, R₁ to R₈, each independently, represent hydrogen,deuterium, or a (C6-C30)aryl unsubstituted or substituted with at leastone of deuterium(s) and a (C6-C30)aryl(s). According to one embodimentof the present disclosure, R₁ to R₈, each independently, representhydrogen, deuterium, or a (C6-C25)aryl unsubstituted or substituted witha (C6-C30)aryl(s). According to another embodiment of the presentdisclosure, R₁ to R₈, each independently, represent hydrogen, deuterium,or an unsubstituted (C6-C18)aryl. R₁ to R₈, may be the same as ordifferent from one another. For example, R₁ to R₈, each independently,may represent hydrogen, deuterium, a phenyl, a naphthyl, or a biphenyl.

According to one embodiment of the present disclosure, the formula 2 maybe represented by the following formula 3.

In formula 3, Ar₂₁ and Ar₂₂, each independently, represent a phenylunsubstituted or substituted with deuterium(s), a biphenyl unsubstitutedor substituted with deuterium(s), a terphenyl unsubstituted orsubstituted with deuterium(s), or a naphthyl unsubstituted orsubstituted with deuterium(s); L₂₁ represents a naphthyleneunsubstituted or substituted with deuterium(s), or a biphenyleneunsubstituted or substituted with deuterium(s); R₁, R₄, R₅, and R₈, eachindependently, represent hydrogen, deuterium, a phenyl unsubstituted orsubstituted with deuterium(s), a biphenyl unsubstituted or substitutedwith deuterium(s), a terphenyl unsubstituted or substituted withdeuterium(s), or a naphthyl unsubstituted or substituted withdeuterium(s); and R₂, R₃, R₈, and R₇, each independently, representhydrogen or deuterium; with the proviso that if both Ar₂₁ and Ar₂₂represent a phenyl, at least one of R₁, R₄, R₅, and R₈ is not hydrogenor deuterium.

The compound represented by formula 1 may be specifically exemplified bythe following compounds, but is not limited thereto.

The compound represented by formula 2 may be specifically exemplified byany one of the following compounds, but is not limited thereto.

The combination of at least one of compounds H1-1 to H1-150 and at leastone of compounds H2-1 to H2-55 may be used in an organicelectroluminescent device.

According to one embodiment of the present disclosure, the presentdisclosure provides an organic electroluminescent compound representedby formula 3. The compound represented by formula 3 may be specificallyexemplified by compounds H2-2 to H2-13, H2-15 to H2-22, H2-24 to H2-28,H2-32 to H2-35, H2-43, H2-46, H2-47, and H2-50 to H2-55, but is notlimited thereto. In addition, the present disclosure may provide anorganic electroluminescent device comprising the organicelectroluminescent compound represented by formula 3.

The compound represented by formula 1 according to the presentdisclosure may be prepared as shown in the following reaction scheme 1and by a synthetic method known to one skilled in the art. For example,the compound represented by formula 1 can be prepared by referring toKorean Patent Appl. Laid-Open Nos. 2015-0135109 (published on Dec. 2,2015), 2016-0099471 (published on Aug. 22, 2016), 2015-0077513(published on Jul. 8, 2015), and 2017-0129599 (published on Nov. 27,2017), but is not limited thereto.

The compound represented by formula 2 or 3 according to the presentdisclosure may be prepared as shown in the following reaction scheme 2and by a synthetic method known to one skilled in the art, but are notlimited thereto.

In reaction schemes 1 and 2, Ar₁, L₁, Ra, R₁₈ to R₂₀, h to j, R₁ to R₈,L₃, and HAr are as defined in formulas 1, 1-4, and 2, Hal represents I,Br, Cl, ONf (nonafluorobutanesulfonyl), or OTf (triflate).

Although illustrative synthesis examples of the compounds represented byformulas 1 to 3 are described above, one skilled in the art will be ableto readily understand that all of them are based on a Buchwald-Hartwigcross-coupling reaction, an N-arylation reaction, H-mont-mediatedetherification reaction, a Miyaura borylation reaction, a Suzukicross-coupling reaction, an intramolecular acid-induced cyclizationreaction, a Pd(ll)-catalyzed oxidative cyclization reaction, a Grignardreaction, a Heck reaction, a Cyclic Dehydration reaction, an SN₁substitution reaction, an SN₂ substitution reaction, aPhosphine-mediated reductive cyclization reaction, etc., and thereactions above proceed even when substituents which are defined informulas 1 to 3 above, but are not specified in the specific synthesisexamples, are bonded. For example, the compounds of formulas 1 to 3containing deuterium may be prepared by treating the non-deuteratedcompounds with a deuterated solvent or D6-benzene in the presence of anH/D exchange catalyst such as a Lewis acid, e.g., aluminium trichlorideor ethyl aluminium chloride, a trifluoromethanesulfonic acid, or atrifluoromethanesulfonic acid-D. In addition, the degree of deuterationcan be controlled by adjusting the reaction conditions such as thereaction temperature and time, the equivalent of the acid, etc.

The organic electroluminescent device according to the presentdisclosure comprises an anode, a cathode, and at least one organic layerbetween the anode and the cathode. The organic layer may comprise aplurality of organic electroluminescent materials in which the compoundrepresented by formula 1 is comprised as a first organicelectroluminescent material, and the compound represented by formula 2is comprised as a second organic electroluminescent material. Accordingto one embodiment of the present disclosure, the organicelectroluminescent device comprises an anode, a cathode, and at leastone light-emitting layer between the anode and the cathode, and thelight-emitting layer comprises a compound(s) represented by formula 1,and a compound(s) represented by formula 2.

The electrode may be a transflective electrode or a reflectiveelectrode, and may be a top emission type, a bottom emission type, or aboth-sides emission type, depending on the materials. The hole injectionlayer may be further doped with a p-dopant, and the electron injectionlayer may be further doped with an n-dopant.

The light-emitting layer comprises a host and a dopant. The hostcomprises a plurality of host materials. The compound represented byformula 1 may be comprised as a first host compound of the plurality ofhost materials, and the compound represented by formula 2 may becomprised as a second host compound of the plurality of host materials.The weight ratio of the first host compound to the second host compoundis in the range of about 1:99 to about 99:1, preferably about 10:90 toabout 90:10, more preferably about 30:70 to about 70:30, even morepreferably about 40:60 to about 60:40, and still more preferably about50:50. When two or more materials are included in one layer, they may bemixture-evaporated to form a layer, or may be separately co-evaporatedat the same time to form a layer.

The light-emitting layer is a layer from which light is emitted, and canbe a single layer or a multi-layer in which two or more layers arestacked. In the plurality of host materials according to the presentdisclosure, the first and second host materials may both be comprised inone layer, or may be respectively comprised in different light-emittinglayers. According to one embodiment of the present disclosure, thedoping concentration of the dopant compound with respect to the hostcompound in the light-emitting layer is less than about 20 wt%.

The organic electroluminescent device of the present disclosure mayfurther comprise at least one layer selected from a hole injectionlayer, a hole transport layer, a hole auxiliary layer, a light-emittingauxiliary layer, an electron transport layer, an electron injectionlayer, an interlayer, an electron buffer layer, a hole blocking layer,and an electron blocking layer. According to one embodiment of thepresent disclosure, the organic electroluminescent device may furthercomprise amine-based compounds in addition to the plurality of hostmaterials of the present disclosure as at least one of a hole injectionmaterial, a hole transport material, a hole auxiliary material, alight-emitting material, a light-emitting auxiliary material, and anelectron blocking material. Also, according to one embodiment of thepresent disclosure, the organic electroluminescent device of the presentdisclosure may further comprise azine-based compounds in addition to theplurality of host materials of the present disclosure as at least one ofan electron transport material, an electron injection material, anelectron buffer material, and a hole blocking material.

The dopant comprised in the organic electroluminescent device accordingto the present disclosure may be at least one phosphorescent orfluorescent dopant, preferably at least one phosphorescent dopant. Thephosphorescent dopant materials applied to the organicelectroluminescent device according to the present disclosure are notparticularly limited, but may be selected from metallated complexcompounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt),may be preferably selected from ortho-metallated complex compounds ofiridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and may bemore preferably an ortho-metallated iridium complex compound.

The dopant comprised in the organic electroluminescent device of thepresent disclosure may include the compound represented by the followingformula 101, but is not limited thereto.

In formula 101, L is selected from the following structures 1 and 2:

-   R₁₀₀ to R₁₀₃, each independently, represent hydrogen, deuterium, a    halogen, a (C1-C30)alkyl unsubstituted or substituted with    deuterium(s) and/or a halogen(s), a substituted or unsubstituted    (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a    cyano, a substituted or unsubstituted (3- to 30-membered)heteroaryl,    or a substituted or unsubstituted (C1-C30)alkoxy; or may be linked    to an adjacent one(s) of R₁₀₀ to R₁₀₃ to form a ring(s), e.g., a    substituted or unsubstituted, quinoline, benzofuropyridine,    benzothienopyridine, indenopyridine, benzofuroquinoline,    benzothienoquinoline, or indenoquinoline ring, together with    pyridine;-   R₁₀₄ to R₁₀₇, each independently, represent hydrogen, deuterium, a    halogen, a (C1-C30)alkyl unsubstituted or substituted with    deuterium(s) and/or a halogen(s), a substituted or unsubstituted    (C3-C30)cycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a    substituted or unsubstituted (3- to 30-membered)heteroaryl, a cyano,    or a substituted or unsubstituted (C1-C30)alkoxy; or may be linked    to an adjacent one(s) of R₁₀₄ to R₁₀₇ to form a ring, e.g., a    substituted or unsubstituted, naphthalene, fluorene,    dibenzothiophene, dibenzofuran, indenopyridine, benzofuropyridine or    benzothienopyridine ring, together with benzene;-   R₂₀₁ to R₂₁₁, each independently, represent hydrogen, deuterium, a    halogen, a (C1-C30)alkyl unsubstituted or substituted with    deuterium(s) and/or a halogen(s), a substituted or unsubstituted    (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl;    or may be linked to an adjacent one(s) of R₂₀₁ to R₂₁₁ to form a    ring; and-   n′ represents an integer of 1 to 3.

The specific examples of the dopant compound are as follows, but are notlimited thereto.

In order to form each layer of the organic electroluminescent device ofthe present disclosure, dry film-forming methods such as vacuumevaporation, sputtering, plasma, and ion plating methods, or wetfilm-forming methods such as ink jet printing, nozzle printing, slotcoating, spin coating, dip coating, and flow coating methods can beused.

In a wet film-forming method, a thin film can be formed by dissolving ordiffusing materials forming each layer into any suitable solvent such asethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvent can beany solvent where the materials forming each layer can be dissolved ordiffused, and where there are no problems in film-formation capability.

In addition, the compound represented by formula 1 and the compoundrepresented by formula 2 or 3 may be film-formed in the above-listedmethods, commonly by a co-evaporation process or a mixture-evaporationprocess. The co-evaporation is a mixed deposition method in which two ormore materials are placed in a respective individual crucible source andan electric current is applied to both cells at the same time toevaporate the materials. The mixture-evaporation is a mixed depositionmethod in which two or more materials are mixed in one crucible sourcebefore evaporating them, and an electric current is applied to the cellto evaporate the materials.

The organic electroluminescent materials according to the presentdisclosure may be used as light-emitting materials for a white organiclight-emitting device. The white organic light-emitting device has beensuggested to have various structures such as a side-by-side structure ora stacking structure depending on the arrangement of R (red), G (green)or YG (yellow green), and B (blue) light-emitting parts, or a colorconversion material (CCM) method, etc., and the present disclosure mayalso be applied to such white organic light-emitting device.

In addition, the organic electroluminescent materials according to thepresent disclosure may also be used in an organic electroluminescentdevice comprising a quantum dot (QD).

The present disclosure may provide a display system comprising theplurality of host materials of the present disclosure. In addition, itis possible to produce a display system or a lighting system by usingthe organic electroluminescent device of the present disclosure.Specifically, it is possible to produce a display system, e.g., adisplay system for smartphones, tablets, notebooks, PCs, TVs, or cars,or a lighting system, e.g., an outdoor or indoor lighting system, byusing the organic electroluminescent device of the present disclosure.

Hereinafter, the preparation method of the compound of the presentdisclosure and the properties thereof will be explained in detail withreference to the representative compounds of the present disclosure.However, the present disclosure is not limited by the followingexamples.

Example 1: Preparation of Compound H1-131

Synthesis of Compound 1

7H-dibenzo[c,g]carbazole (60 g, 224 mmol) was dissolved in 900 mL ofN,N-dimethylformamide (DMF) in a flask, and the mixture was cooled to 0°C. and stirred. N-bromosuccinimide (NBS) (36 g, 202 mmol) was dissolvedin 220 mL of DMF, and was then added dropwise to the mixture for 2.5hours. The resulting mixture was stirred at room temperature for 2hours. After completion of the reaction, the reaction product was washedwith an aqueous Na₂S₂O₃ solution and water, an organic layer wasextracted with ethyl acetate, and the residual moisture was removed withMgSO₄. The residue was dried and separated by a silica filter to obtaincompound 1 (79 g, yield: 79%).

Synthesis of Compound 2

Compound 1 (76 g, 220 mmol), iodobenzene (90 g, 439 mmol), Cul (20.90 g,110 mmol), ethylenediamine (EDA) (13 g, 110 mmol), and K₃PO₄ (139 g, 659mmol) were added to 1.1 L of toluene, and the mixture was stirred underreflux for 2.5 hours. MeOH was added to the mixture, and the resultingsolid was filtered under reduced pressure. The residue was separated bycolumn chromatography to obtain compound 2 (55.1 g, yield: 60%).

Synthesis of Compound 3

Compound 2 (54.6 g, 129 mmol), 2-chloroaniline (20 g, 155 mmol),Pd(OAc)₂ (2.9 g, 13 mmol), P(t-Bu)₃ (5.2 g, 26 mmol), sodiumtert-butoxide (NaOt-Bu) (31 g, 323 mmol), and 650 mL of toluene werestirred under reflux for 4 hours. The mixture was cooled to roomtemperature and NH₄Cl (aq) was added thereto. The reaction product wasextracted with ethyl acetate (EA) and dried with magnesium sulfate. Theresidue was distilled under reduced pressure, and separated by columnchromatography to obtain compound 3 (47.9 g, yield: 79%).

Synthesis of Compound 4

Compound 3 (48 g, 103 mmol), Pd(OAc)₂ (2.3 g, 10 mmol),ligand(tricyclohexylphosphonium tetrafluoroborate) (7.6 g, 21 mmol),Cs₂CO₃ (100 g, 308 mmol), and 400 mL of N,N-dimethylacetamide (DMA) werestirred under reflux for 1 hour. The reaction product was cooled to roomtemperature and NH₄Cl (aq) was added thereto. An organic layer wasextracted with methylene chloride (MC) and dried with magnesium sulfate.The residue was distilled under reduced pressure, and separated bycolumn chromatography to obtain compound 4 (44 g, yield: 79%).

Synthesis of Compound H1-131

Compound 4 (5 g, 12 mmol), iodobenzene (3.5 g, 17 mmol), Cul (1.1 g, 6mmol), 1,2-diaminocyclohexane (2.6 g, 23 mmol), and K₃PO₄ (4.9 g, 23mmol) were added to 60 mL of o-xylene, and the mixture was stirred underreflux for one day. The reaction product was cooled to room temperatureand was subjected to celite filter using MC. The filtrate was distilledunder reduced pressure, and separated by column chromatography usingMC/Hex to obtain compound H1-131 (1.3 g, yield: 22%).

¹H NMR (600 MHz,DMSO,δ) 9.16-9.15(d,1H), 8.99-8.98(d,1H),8.14-8.13(d,1H), 7.94-7.93(d,1H), 7.94-7.68(m,9H), 7.65-7.61(m,3H),7.60-7.54(m,3H), 7.25-7.21(m,2H), 7.08-7.07(d,1H), 6.78-6.76(m,1H)5.95-5.94(d,1H)

MW UV PL M.P. H1-131 508.62 342 nm 427 nm 184° C.

Example 2: Preparation of Compound H1-132

Compound 4 (7 g, 16 mmol), 2-bromonaphthalene (6.7 g, 32 mmol), Cul (1.5g, 8 mmol), 1,2-diaminocyclohexane (3.7 g, 32 mmol), and K₃PO₄ (10.3 g,49 mmol) were added to 80 mL of o-xylene, and the mixture was stirredunder reflux for one day. The reaction product was cooled to roomtemperature and was subjected to celite filter using MC. The filtratewas distilled under reduced pressure, and separated by columnchromatography using MC/Hex to obtain compound H1-132 (1.3 g, yield:22%).

¹H NMR (600 MHz,DMSO,δ) 9.17-9.15(d,1H), 9.00-8.99(d,1H),8.31-8.30(m,2H), 8.20-8.18(d,1H), 8.15-8.14(d,1H), 8.11-8.10(d,1H),7.95-7.94(d,1H), 7.83-7.79(m,5H), 7.73-7.69(m,4H), 7.60-7.57(m,4H),7.21-7.18(m,2H), 7.14-7.13(d,1H), 6.78-6.77(t,1H) 5.98-5.96(d,1H)

MW UV PL M.P. H1-132 558.68 340 nm 431 nm 263° C.

Example 3: Preparation of Compound H1-134

Synthesis of Compound 5

Compound 1 (15 g, 220 mmol), 3-iodo-1,1′-biphenyl (18 g, 65 mmol),Cul(4.1 g, 22 mmol), ethylenediamine (2.6 g, 43 mmol), and K₃PO₄ (23 g, 108mmol) were added to 216 mL of toluene, and the mixture was stirred underreflux for 4 hours. MeOH was added to the mixture, and the resultingsolid was filtered under reduced pressure. The filtrate was separated bycolumn chromatography to obtain compound 5 (16 g, yield: 74%).

Synthesis of Compound 6

Compound 5 (15 g, 30 mmol), 2-chloroaniline (7.7 g, 60 mmol), Pd(OAc)₂(0.67 g, 3 mmol), P(t-Bu)₃ (1.2 g, 6 mmol), NaOt-Bu (7.2 g, 75 mmol),and 150 mL of toluene were stirred under reflux for 2 hours. Thereaction product was cooled to room temperature and NH₄Cl (aq) was addedthereto. An organic layer was extracted with EA and dried with magnesiumsulfate. The residue was distilled under reduced pressure, and separatedby column chromatography to obtain compound 6 (10.1 g, yield: 62%).

Synthesis of Compound 7

Compound 6 (10 g, 18 mmol), Pd(OAc)₂ (0.41 g, 1.8 mmol),ligand(tricyclohexylphosphonium tetrafluoroborate) (1.35 g, 3.7 mmol),Cs₂CO₃ (18 g, 55 mmol), and 92 mL of DMA were stirred under reflux for 1hour. The reaction product was cooled to room temperature and NH₄Cl (aq)was added thereto. An organic layer was extracted with MC and dried withmagnesium sulfate. The residue was distilled under reduced pressure, andseparated by column chromatography to obtain compound 7 (7.1 g, yield:76%).

Synthesis of Compound H1-134

Compound 7 (6.7 g, 13 mmol), 3-iodo-1,1′-biphenyl (7.4 g, 26 mmol), Cupowder (0.42 g, 7 mmol), and K₂CO₃ (3.6 g, 26 mmol) were added to 70 mLof o-dichlorobenzene, and the mixture was stirred under reflux for oneday. The reaction product was cooled to room temperature and wassubjected to celite filter using MC. The filtrate was distilled underreduced pressure, and separated by column chromatography using MC/Hex toobtain compound H1-134 (3.1 g, yield: 36%).

¹H NMR (600 MHz,DMSO,δ) 9.18-9.17(d,1H), 9.01-9.00(d,1H),8.16-8.15(d,1H), 8.11-8.09(d,1H), 8.06-8.05(m,2H), 8.00-7.79(m,7H),7.73-7.57(m,8H), 7.48-7.38(m, 6H), 7.30-7.28(t,1H), 7.22-7.18(m,2H),6.80-6.78(t,1H), 6.07-6.06(d,1H)

MW M.P. H1-134 660.82 259° C.

Example 4: Preparation of Compound H1-133

Compound 4 (4 g, 9.25 mmol), 3-iodo-1,1′-biphenyl (3.1 g, 11.1 mmol),tris(dibenzylideneacetone)dipalladium(0) (Pd₂(dba)₃) (0.42 g, 0.46mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos) (0.38 g,0.92 mmol), and NaOt-Bu (2.2 g, 23.13 mmol) were added to 46 mL ofo-xylene, and the mixture was stirred under reflux for one day. Thereaction product was extracted with MC, distilled under reducedpressure, and separated by column chromatography using MC/Hex to obtaincompound H1-133 (1.2 g, yield: 23%).

¹H NMR (600 MHz,DMSO,δ) 9.17-9.15(d,1H), 9.00-8.98(d,1H),8.15-8.13(d,1H), 8.07-8.06(d,1H), 7.98(m,1H), 7.95-7.94(d,1H),7.88-7.86(t,1H), 7.82-7.80(m,7H), 7.71-7.67(m,2H), 7.65-7.61(m,2H),7.60-7.55(m,2H), 7.49-7.47(t,2H), 7.42-7.39(t,1H), 7.30-7.27(t,1H),7.26-7.23(t,1H), 7.20-7.19(d,1H), 6.80-6.77(t,1H), 5.97-5.95(d,1H)

MW M.P. H1-133 584.7 249.6° C.

Example 5: Preparation of Compound H1-135

Synthesis of Compound 1

7H-dibenzo[c,g]carbazole (50 g, 187 mmol) was dissolved in 750 mL of DMFin a flask, and the mixture was cooled to 0° C. and stirred. NBS (30 g,168 mmol) was dissolved in 250 mL of DMF, and was then added dropwise tothe mixture for 1 hour. The resulting mixture was stirred at roomtemperature for 2 hours. After completion of the reaction, the reactionproduct was washed with an aqueous Na₂S₂O₃ solution and water, anorganic layer was extracted with ethyl acetate, and the residualmoisture was removed with MgSO₄. The residue was dried and separated bya silica filter to obtain compound 1 (40 g, yield: 62%).

Synthesis of Compound 8

Compound 1 (11 g, 32 mmol), 4-iodo-1,1′-biphenyl (17.8 g, 64 mmol), Cul(3.0 g, 15.9 mmol), ethylenediamine (1.91 g, 31.8 mmol), and K₃PO₄ (20.3g, 95 mmol) were added to 160 mL of toluene, and the mixture was stirredunder reflux for 4 hours. MeOH was added to the mixture, and theresulting solid was filtered under reduced pressure. The filtrate wasseparated by column chromatography to obtain compound 8 (13.0 g, yield:82%).

Synthesis of Compound 9

Compound 8 (13.0 g, 26 mmol), 2-chloroaniline (6.7 g, 52 mmol), Pd(OAc)₂(0.59 g, 2.6 mmol), P(t-Bu)₃ (1.1 g, 5.2 mmol), NaOt-Bu (6.3 g, 65mmol), and 130 mL of toluene were stirred under reflux for 4 hours. Thereaction product was cooled to room temperature and NH₄Cl (aq) was addedthereto. An organic layer was extracted with EA and dried with magnesiumsulfate. The residue was distilled under reduced pressure, and separatedby column chromatography to obtain compound 9 (9.2 g, yield: 65%).

Synthesis of Compound 10

Compound 9 (9.2 g, 17 mmol), Pd(OAc)₂ (0.38 g, 2 mmol),ligand(tricyclohexylphosphonium tetrafluoroborate) (1.2 g, 3 mmol),Cs₂CO₃ (138 g, 42 mmol), and 70 mL of DMA were stirred under reflux for1 hour. The reaction product was cooled to room temperature and NH₄Cl(aq) was added thereto. The resulting solid was distilled under reducedpressure, and separated by column chromatography to obtain compound 10(6.0 g, yield: 70%).

Synthesis of Compound H1-135

Compound 10 (6 g, 12 mmol), 2-bromonaphthalene (4.9 g, 24 mmol), Cul(1.1 g, 6 mmol), 1,2-diaminocyclohexane (2.7 g, 24 mmol), and K₃PO₄ (7.5g, 35 mmol) were added to 60 mL of o-xylene, and the mixture was stirredunder reflux for one day. The reaction product was cooled to roomtemperature. Then, an organic layer was separated by adding ethylacetate and water, and dried with magnesium sulfate. The residue wassubjected to celite filter using MC. The filtrate was distilled underreduced pressure, and separated by column chromatography using MC/Hex toobtain compound H1-135 (2.1 g, yield: 28%).

¹H NMR (600 MHz,DMSO,δ) 9.18-9.17(d,1H), 9.01-8.99(d,1H),8.33-8.31(m,2H), 8.20-8.19(d,1H), 8.17-8.15(d,1H), 8.12-8.08(m,3H),7.98-7.97(d,1H), 7.93-7.89(m,4H), 7.70-7.68(m,5H), 7.63-7.57(m,5H)7.50-7.48(t,1H), 7.22-7.19(t,1H), 7.15-7.13(d,1H), 6.77-6.74(td, 1H),6.16-6.15(d, 1H)

MW M.P. H1-135 508.62 294° C.

Example 6: Preparation of Compound H1-11

Compound 1-1 (7 g, 13 mmol), dibenzo[b,d]furan-1-ylboronic acid (3 g,14.3 mmol), K₂CO₃ (5.4 g, 39 mmol), and Pd(PPh₃)₄ (0.75 g, 0.65 mmol)were dissolved in 30 mL of H₂O, 60 mL of toluene, and 30 mL of EtOH in aflask, and the mixture was refluxed at 120° C. for 3 hours. Aftercompletion of the reaction, an organic layer was extracted with ethylacetate, and the residual moisture was removed with magnesium sulfate.The residue was dried and separated by column chromatography to obtaincompound H1-11 (5.7 g, yield: 70%).

¹H NMR (600 MHz,CDCl₃,δ) 9.305 (s,1H), 9.049-9.035(d, J=8.4 Hz, 1H),8.379-8.367(d, J=7.2 Hz, 1H), 8.022-8.008(d, J=8.4 Hz, 1H)7.816-7.705(m, 6H), 7.699-7.392(m, 16H) 7.195-7.127(m,2 H)

MW M.P. H1-11 642.73 154° C.

Example 7: Preparation of Compound H1-54

Compound 1-2 (5.7 g, 10.6 mmol), dibenzo[b,d]furan-1-ylboronic acid (2.5g, 11.7 mmol), K₂CO₃ (4.4 g, 31.8 mmol), and Pd(PPh₃)₄ (0.61 g, 0.653mmol) were dissolved in 30 mL of H₂O, 60 mL of toluene, and 30 mL ofEtOH in a flask, and the mixture was refluxed at 120° C. for 3 hours.After completion of the reaction, an organic layer was extracted withethyl acetate, and the residual moisture was removed with magnesiumsulfate. The residue was dried and separated by column chromatography toobtain compound H1-54 (1.2 g, yield: 18%).

¹H NMR (600 MHz,CDCl₃,δ) 8.880 (s,1H), 8.378-8.364(d, J=8.4 Hz, 1H),8.297-8.284(d, J=7.8 Hz, 1H), 8.000-7.987(d, J=7.8 Hz, 1H)7.777-7.702(m, 5H),7.615-7.332(m, 15H), 7.189-7.127(m, 4H)

MW M.P. H1-54 624.73 239° C.

Example 8: Preparation of Compound H1-53

Compound 1-2 (5.0 g, 9.3 mmol), dibenzo[b,d]furan-4-ylboronic acid (2.2g, 10.2 mmol), Pd(PPh₃)₄ (0.54 g, 0.47 mmol), and K₂CO₃ (2.6 g, 18.6mmol) were dissolved in 20 mL of toluene, 8 mL of EtOH, and 10 mL of H₂Oin a flask, and the mixture was refluxed at 120° C. for 3 hours. Aftercompletion of the reaction, an organic layer was extracted with ethylacetate, and the residual moisture was removed with magnesium sulfate.The residue was dried and separated by column chromatography to obtaincompound H1-53 (3.5 g, yield: 60%).

¹H NMR (600 MHz,DMSO₃,δ) 9.210(s,1H), 8.516-8.502(d,1H), 8.408-8.395(d,1H), 8.219-8.198(m,2H), 8.115-8.109(t,1H), 8.087-8.073(d,1H),8.040-8.028(d, 1H), 7.856-7.842(d,1H), 7.833-7.807(t,1H),7.733-7.611(m,9H), 7.562-7.531(m,2H), 7.515-7.490(t,1H),7.451-7.426(t,1H), 7.293-7.279(d,1H), 7.258-7.232(t,1H), 7.119(s,1H)

MW M.P. H1-53 624.7 161° C.

Example 9: Preparation of Compound H1-13

7-phenyl-7,9-dihydrobenzo[g]indolo[2,3-b]carbazole (3.6 g, 9.285 mmol),1-(4-bromophenyl)dibenzo[b,d]furan (3 g, 9.285 mmol), Cul (0.08 g, 0.464mmol), EDA (0.5 g, 9.285 mmol), and K₃PO₄ (4.9 g, 23.21 mmol) were addedto 50 mL of xylene, and the mixture was stirred for one day. Aftercompletion of the reaction, the reaction product was cooled to roomtemperature, and extracted with distilled water and MeOH. The extractedproduct was separated by column chromatography using MC/Hex to obtaincompound H1-13 (2.7 g, yield: 47%).

¹H NMR (DMSO-d₆) δ: 9.69 (s, 1H), 9.26 (d, J = 8.3 Hz, 1H), 8.69 (dd, J= 7.7, 1.2 Hz, 1H), 8.14 (dd, J = 8.0, 1.1 Hz, 1H), 7.97 (d, J = 8.8 Hz,1H), 7.92 (s, 4H), 7.88 (ddd, J = 8.2, 6.9, 1.3 Hz, 1H), 7.82 - 7.76 (m,4H), 7.73 (t, J = 7.8 Hz, 2H), 7.70 - 7.48 (m, 8H), 7.48 - 7.44 (m, 2H),7.42 (td, J = 7.3, 1.0 Hz, 1H), 7.26 - 7.20 (m, 1H)

MW M.P. H1-13 624.7 309.7° C.

Example 10: Preparation of Compound H1-5

7-phenyl-7,9-dihydrobenzo[g]indolo[2,3-b]carbazole (7.6 g, 18.88 mmol),3-chloro-1,1′:2′, 1 “-terphenyl (5 g, 18.88 mmol), Pd₂(dba)₃ (0.86 g,0.940 mmol), NaOt-Bu (4.5 g, 47.22 mmol), and P(t-Bu)₃ (0.38 g, 1.888mmol) were added to 100 mL of toluene, and the mixture was stirred forone day. After completion of the reaction, the reaction product wascooled to room temperature, and extracted with distilled water and MeOH.The extracted product was separated by column chromatography usingMC/Hex to obtain compound H1-5 (0.7 g, yield: 6.2%).

¹H NMR (DMSO-d₆) δ: 9.58 (s, 1H), 9.20 (d, J = 8.4 Hz, 1H), 8.57 (d, J =7.8 Hz, 1H), 8.11 (d, J = 8.3 Hz, 1H), 7.94 (d, J = 8.9 Hz, 1H), 7.84(ddd, J = 8.3, 6.8, 1.3 Hz, 1H), 7.72 (d, J = 6.2 Hz, 4H), 7.64 - 7.47(m, 8H), 7.44 (dt, J = 6.0, 1.9 Hz, 1H), 7.40 - 7.17 (m, 10H), 6.50 (d,J = 7.9 Hz, 1H)

MW M.P. H1-5 610.7 194.6° C.

Example 11: Preparation of Compound H1-19

7-phenyl-7,9-dihydrobenzo[g]indolo[2,3-b]carbazole (5.1 g, 13 mmol),9-(3-bromophenyl)-9H-carbazole (4.7 ymmol), Pd₂(dba)₃ (0.604 g, 0.66mmol), SPhos (0.546 g, 1.33 mmol), and NaOt-Bu (y g, 33.3 mmol) wereadded to 50 mL of xylene in a flask, and the mixture was stirred underreflux at 190° C. for 2 hours. After completion of the reaction, anorganic layer was extracted with EA, dried with MgSO₄, and separated bycolumn chromatography. Then, MeOH was added to the separated product,and the resulting solid was filtered under reduced pressure to obtaincompound H1-19 (4.4 g, yield: 53.0%).

¹H NMR (600 MHz, DMSO-d₆, δ) 9.66 (s, 1H), 9.24 (d, J = 8.4 Hz, 1H),8.66 (d, J = 7.7 Hz, 1H), 8.26 (d, J = 7.8 Hz, 2H), 8.13 (d, J = 8.1 Hz,1H), 8.01 - 7.94 (m, 2H), 7.91 - 7.84 (m, 3H), 7.79 (dd, J = 8.2, 1.8Hz, 1H), 7.77 - 7.74 (m, 2H), 7.69 (t, J = 7.6 Hz, 2H), 7.62 - 7.55 (m,3H), 7.53 (d, J = 8.1 Hz, 1H), 7.49 - 7.45 (m, 2H), 7.39 (dd, J = 14.4,6.9 Hz, 5H) 7.31 (t, J = 7.5 Hz, 2H)

MW M.P. H1-19 623.76 240° C.

Example 12: Preparation of Compound H1-6

7-phenyl-7,9-dihydrobenzo[g]indolo[2,3-b]carbazole (5.0 g, 13 mmol),4′-bromo-1,1′:3′,1″-terphenyl (6.06 g, 20 mmol), Cu powder (1.307 g,0.65 mmol), and K₂CO₃ (3.4 g, 26 mmol) were added to 60 mL ofo-dichlorobenzene (o-DCB) in a flask, and the mixture was stirred underreflux at 230° C. for 12 hours. After completion of the reaction, anorganic layer was extracted with EA, dried with MgSO₄, and separated bycolumn chromatography. Then, MeOH was added to the separated product,and the resulting solid was filtered under reduced pressure to obtaincompound H1-6 (1.3 g, yield: 16.3%).

¹H NMR (600 MHz, DMSO-d₆, δ) 9.51 (s, 1H), 9.16 (d, J = 8.3 Hz, 1H),8.57 (d, J = 7.8 Hz, 1H), 8.10 (d, J = 8.0 Hz, 1H), 7.98 - 7.85 (m, 6H),7.83 (t, J = 7.6 Hz, 1H), 7.76 (s, 1H), 7.70 (d, J = 8.1 Hz, 1H), 7.61 -7.51 (m, 5H), 7.51 - 7.42 (m, 3H), 7.38 (t, J = 7.8 Hz, 1H), 7.31 (t, J= 7.3 Hz, 1H), 7.25 (d, J = 8.0 Hz, 1H), 7.13 - 7.06 (m, 4H), 7.03 (d, J= 6.8 Hz, 1H), 6.79 (s, 1H)

MW M.P. H1-6 610.74 296° C.

Example 13: Preparation of Compound H1-22

Synthesis of Compound 11

7-phenyl-7,9-dihydrobenzo[g]indolo[2,3-b]carbazole (10 g, 26.14 mmol),1-bromo-3-iodobenzene (14.8 g, 52.29 mmol), Cul (2.5 g, 13.07 mmol), EDA(1.57 g, 26.14 mmol), and K₃PO₄ (13.8 g, 65.36 mmol) were added to 130mL of toluene, and the mixture was stirred for one day. After completionof the reaction, the reaction product was cooled to room temperature,and extracted with distilled water and MeOH. The extracted product wasseparated by column chromatography using MC/Hex to obtain compound 11 (9g, yield: 64%).

Synthesis of Compound 12

Compound 11 (9 g, 16.74 mmol) was added to 85 mL of THF, and n-BuLi (2.5M) (8.7 mL, 21.77 mmol) was then slowly added thereto while stirring at-78° C. for 1 hour. B(Oi-pr)₃ (5.7 mL, 25.12 mmol) was added to themixture, and then stirred for one day. After completion of the reaction,NH₄Cl and distilled water were added to the reaction product, and themixture was stirred for 30 minutes. Next, the resulting product wasextracted with distilled water and EA, and an organic layer wasconcentrated to obtain compound 12 (6.8 g, yield: 80%).

Synthesis of Compound H1-22

Compound 12 (6.8 g, 13.53 mmol), 4-bromo-9,9-dimethyl-9H-fluorene (3.7g, 13.53 mmol), Pd(PPh₃)₄ (0.8 g, 0.676 mmol), and K₂CO₃ (3.7 g, 27.07mmol) were added to 60 mL of toluene, 15 mL of EtOH, and 15 mL ofdistilled water, and the mixture was stirred under reflux for 3 hours.After completion of the reaction, the reaction product was cooled toroom temperature, and extracted with distilled water and EA. An organiclayer was distilled under reduced pressure, and separated by columnchromatography using MC/Hex to obtain compound H1-22 (1.5 g, yield:17%).

¹H NMR (DMSO-d₆) δ: 9.64 (s, 1H), 9.22 (d, J = 8.4 Hz, 1H), 8.64 (dt, J= 7.6, 0.9 Hz, 1H), 8.14 - 8.10 (m, 1H), 7.94 (d, J = 8.9 Hz, 1H),7.90-7.77(m, 3H), 7.68 (s, 3H), 7.65-7.53(m, 7H), 7.53-7.33(m, 6H),7.27(td,J=7.4, 1.1 Hz, 1H), 7.17 (d,J=7.6 Hz, 1H), 6.92(d,J=47.9 Hz,2H), 1.49 (d, J=17.3 Hz, 6H)

MW M.P. H1-22 650.8 166.3° C.

Example 14: Preparation of Compound H1-4

7-phenyl-7,9-dihydrobenzo[g]indolo[2,3-b]carbazole (5 g, 13.07 mmol),4-bromo-1,1′:2′, 1 “-terphenyl (4 g, 13.07 mmol), Pd₂(dba)₃ (0.6 g,0.653 mmol), NaOt-Bu (3.8 g, 39.21 mmol), and SPhos (0.5 g, 1.307 mmol)were added to 70 mL of o-xylene, and the mixture was stirred for oneday. After completion of the reaction, the reaction product was cooledto room temperature, and extracted with distilled water and MeOH. Theextracted product was separated by column chromatography using MC/Hex toobtain compound H1-4 (6.3 g, yield: 78%).

NMR (DMSO-d₆) δ: 9.63 (s, 1H), 9.23 (d, J = 8.3 Hz, 1H), 8.63 (dd, J =7.7, 1.1 Hz, 1H), 8.12 (d, J = 8.2 Hz, 1H), 7.95 (d, J = 8.9 Hz, 1H),7.85 (ddd, J = 8.2, 6.8, 1.4 Hz, 1H), 7.79 - 7.73 (m, 2H), 7.72 - 7.66(m, 3H), 7.60 - 7.47 (m, 8H), 7.44 (ddd, J = 8.2, 7.1, 1.3 Hz, 1H), 7.38-7.33 (m, 3H), 7.32 - 7.24 (m, 2H), 7.22 - 7.14 (m, 5H)

MW M.P. H1-4 610.7 288° C.

Example 15: Preparation of Compound H1-12

Synthesis of Compound 13

Dibenzo[b,d]thiophene-1-ylboronic acid (20 g, 87.71 mmol),1-bromo-3-iodobenzene (50 g, 175.4 mmol), Pd(PPh₃)₄ (5 g, 4.385 mmol),and Na₂CO₃ (18 g, 175.4 mmol) were added to 360 mL of toluene, 90 mL ofdistilled water, and 90 mL of EtOH, and the mixture was stirred underreflux for 3 hours. After completion of the reaction, the reactionproduct was cooled to room temperature, and extracted with distilledwater and EA. An organic layer was distilled under reduced pressure, andseparated by column chromatography using Hex to obtain compound 13 (20g, yield: 67%).

Synthesis of Compound H1-12

Compound 13 (4.4 g, 13.07 mmol),7-phenyl-7,9-dihydrobenzo[g]indolo[2,3-b]carbazole (5 g, 13.07 mmol),Pd₂(dba)₃ (0.6 g, 0.653 mmol), SPhos (0.5 g, 1.307 mmol), and NaOt-Bu(3.7 g, 39.21 mmol) were added to 70 mL of o-xylene, and the mixture wasstirred under reflux for 2 hours. After completion of the reaction, thereaction product was cooled to room temperature, and extracted withMeOH. The extracted product was separated by column chromatography usingMC/Hex to obtain compound H1-12 (5.1 g, yield: 60%).

¹H NMR (DMSO-d₆) δ: 9.63 (s, 1H), 9.22 (d, J = 8.4 Hz, 1H), 8.64 (dd, J= 7.5, 1.2 Hz, 1H), 8.14 - 8.09 (m, 2H), 8.07 (dt, J = 8.1, 0.9 Hz, 1H),7.94 (d, J = 8.9 Hz, 1H), 7.91 - 7.82 (m, 3H), 7.72 (d, J = 2.0 Hz, 1H),7.67 (d, J = 7.6 Hz, 2H), 7.63 - 7.48 (m, 8H), 7.48 - 7.41 (m, 2H), 7.40(d, J = 6.1 Hz, 1H), 7.36 (td, J = 7.4, 1.0 Hz, 1H), 7.33 (d, J = 7.3Hz, 1H), 7.09 (d, J = 49.0 Hz, 2H)

MW M.P. H1-12 640.7 226.7° C.

Example 16: Preparation of Compound H2-3

Synthesis of Compound 2-1

2-chloro-4,6-di(naphthalene-2-yl)-1,3,5-triazine (20 g, 79.7 mmol),(4-bromonaphthalene-1-yl)boronic acid (32.2 g, 87.7 mmol), Pd(PPh₃)₄(4.6 g, 3.985 mmol), and Cs₂CO₃ (65 g, 199.25 mmol) were added to 400 mLof toluene in a flask, and the mixture was stirred under reflux for 4hours. After completion of the reaction, the reaction product was cooledto room temperature, an organic layer was extracted with ethyl acetate,and the residual moisture was removed with magnesium sulfate. Theresidue was dried, and separated by column chromatography to obtaincompound 2-1 (30 g, yield: 74%).

Synthesis of Compound H2-3

Compound 2-1 (10 g, 19.7 mmol), 9H-carbazole (3.0 g, 17.9 mmol),Pd₂(dba)₃ (0.8 g, 0.9 mmol), SPhos (0.73 g, 1.79 mmol), and NaOt-Bu (4.3g, 44.75 mmol) were dissolved in 90 mL of o-xylene in a flask, and themixture was stirred under reflux for 4 hours. After completion of thereaction, the reaction product was extracted with ethyl acetate, andseparated by column chromatography to obtain compound H2-3 (1.5 g,yield: 13%).

MW M.P. H2-3 624.75 265° C.

Example 17: Preparation of Compound H2-10

Synthesis of Compound 2-2

4-bromo-9H-carbazole (10 g, 40.6 mmol), phenylboronic acid (6.2 g, 48.7mmol), Pd(PPh₃)₄ (2.3 g, 2.03 mmol), and Na₂CO₃ (13 g, 121.8 mmol) wereadded to 200 mL of toluene, 100 mL of ethanol, and 100 mL of water in aflask, and the mixture was stirred under reflux for 3 hours. Aftercompletion of the reaction, the reaction product was cooled to roomtemperature, an organic layer was extracted with ethyl acetate, and theresidual moisture was removed with magnesium sulfate. The residue wasdried, and separated by column chromatography to obtain compound 2-2 (9g, yield: 91%).

Synthesis of Compound H2-10

Compound 2-1 (8.5 g, 13.5 mmol), compound 2-2 (3.0 g, 12.3 mmol),Pd₂(dba)₃ (0.56 g, 0.615 mmol), SPhos (0.51 g, 1.23 mmol), and NaOt-Bu(2.9 g, 30.75 mmol) were dissolved in 60 mL of o-xylene in a flask, andthe mixture was stirred under reflux for 4 hours. After completion ofthe reaction, the reaction product was extracted with ethyl acetate, andseparated by column chromatography to obtain compound H2-10 (2.8 g,yield: 32.5%).

MW M.P. H2-10 700.85 260.3° C.

Example 18: Preparation of Compound H2-8

4-phenyl-9H-carbazole (3.0 g, 12.3 mmol),2-(4-bromonaphthalene-1-yl)-4,6-diphenyl-1,3,5-triazine (5.4 g, 12.3mmol), Pd₂(dba)₃ (0.56 g, 0.62 mmol), SPhos (0.51 g, 1.23 mmol), andNaOt-Bu (2.4 g, 24.7 mmol) were added to 62 mL of o-xylene in a flask,and the mixture was stirred under reflux for 6 hours. After completionof the reaction, the reaction product was cooled to room temperature,and then MeOH was added thereto while stirring at room temperature. Theresulting solid was filtered under reduced pressure, and the filtratewas separated by column chromatography to obtain compound H2-8 (3.3 g,yield: 45%).

MW M.P. H2-8 600.71 254° C.

Example 19: Preparation of Compound H2-2

Compound A (8.0 g, 16.4 mmol), 9H-carbazole (3.0 g, 18.0 mmol),Pd₂(dba)₃ (0.9 g, 0.8 mmol), SPhos (0.7 g, 1.64 mmol), and NaOt-Bu (2.4g, 24.6 mmol) were added to 82 mL of o-xylene in a flask, and themixture was stirred under reflux for 4 hours. After completion of thereaction, the reaction product was extracted with ethyl acetate, andseparated by column chromatography to obtain compound H2-2 (6.0 g,yield: 69%).

MW M.P. H2-2 524.63 245° C.

Example 20: Preparation of Compound H2-11

Synthesis of Compound 2-3

1-bromo-9H-carbazole (10 g, 40.6 mmol), phenylboronic acid (6.2 g, 48.7mmol), Pd(PPh₃)₄ (2.3 g, 2.03 mmol), and Na₂CO₃ (13 g, 121.8 mmol) wereadded to 200 mL of toluene, 100 mL of ethanol, and 100 mL of water in aflask, and the mixture was stirred under reflux for 3 hours. Aftercompletion of the reaction, the reaction product was cooled to roomtemperature, an organic layer was extracted with ethyl acetate, and theresidual moisture was removed with magnesium sulfate. The residue wasdried, and separated by column chromatography to obtain compound 2-3 (9g, yield: 96%).

Synthesis of Compound H2-11

Compound 2-3 (3.0 g, 12.3 mmol), compound A (8 g, 18.5 mmol), Cu powder(0.39 g, 6.15 mmol), and K₂CO₃ (3.4 g, 24.6 mmol) were added to 60 mL ofdichlorobenzene (DCB) in a flask, and the mixture was stirred underreflux for 24 hours. After completion of the reaction, the reactionproduct was cooled to room temperature, and MeOH was added thereto whilestirring at room temperature. The resulting solid was filtered underreduced pressure, and the filtrate was separated by columnchromatography to obtain compound H2-11 (1.1 g, yield: 14.8%).

MW M.P. H2-11 600.23 226.9° C.

Hereinafter, the luminous efficiency and lifetime properties of an OLEDaccording to the present disclosure will be explained in detail.However, the following examples merely illustrate the properties of anOLED according to the present disclosure in detail, but the presentdisclosure is not limited to the following examples.

Device Examples 1-1 to 1-3: Producing an OLED Co-Deposited With a FirstHost Compound and a Second Host Compound According to the PresentDisclosure

An OLED according to the present disclosure was produced as follows: Atransparent electrode indium tin oxide (ITO) thin film (10 Ω/sq) on aglass substrate for an OLED (GEOMATEC CO., LTD., Japan) was subjected toan ultrasonic washing with acetone and isopropyl alcohol, sequentially,and then was stored in isopropanol. The ITO substrate was mounted on asubstrate holder of a vacuum vapor deposition apparatus. Compound HI-1shown in Table 3 below as a first hole injection compound was introducedinto a cell of the vacuum vapor deposition apparatus, and compound HT-1shown in Table 3 below as a first hole transport compound was introducedinto another cell of the vacuum vapor deposition apparatus. The twomaterials were evaporated at different rates to be deposited in a dopingamount of the first hole injection compound of 3 wt% based on the totalamount of the first hole injection compound and the first hole transportcompound to form a first hole injection layer having a thickness of 10nm on the ITO substrate. Next, compound HT-1 was deposited as a firsthole transport layer having a thickness of 80 nm on the first holeinjection layer. Compound HT-2 was then introduced into another cell ofthe vacuum vapor deposition apparatus and was evaporated by applying anelectric current to the cell, thereby forming a second hole transportlayer having a thickness of 60 nm on the first hole transport layer.After forming the hole injection layer and the hole transport layers, alight-emitting layer was formed thereon as follows: The first hostcompound and the second host compound shown in Table 1 below wereintroduced into two cells of the vacuum vapor depositing apparatus,respectively, as hosts, and compound D-39 was introduced into anothercell as a dopant. The two host materials were evaporated at a rate of1:1, and at the same time the dopant material was evaporated atdifferent rates to be deposited in a doping amount of 3 wt% based on thetotal amount of the hosts and dopant to form a light-emitting layerhaving a thickness of 40 nm on the second hole transport layer. Next,compound ET-1 and compound EI-1 as electron transport materials weredeposited at a weight ratio of 50:50 on the light-emitting layer to forman electron transport layer having a thickness of 35 nm. Afterdepositing compound EI-1 as an electron injection layer having athickness of 2 nm on the electron transport layer, an AI cathode havinga thickness of 80 nm was deposited on the electron injection layer byanother vacuum vapor deposition apparatus. Thus, an OLED was produced.All the materials used for producing the OLED were purified by vacuumsublimation at 10⁻⁶ torr.

Comparative Examples 1-1 to 1-3: Producing an OLED Comprising aComparative Compound as a Host

An OLED was produced in the same manner as in Device Example 1-1, exceptthat the second host compound shown in Table 1 below was solely used asa host of the light-emitting layer.

Comparative Example 1-4: Producing an OLED Comprising a ComparativeCompound as a Host

An OLED was produced in the same manner as in Device Example 1-1, exceptthat the first host compound and the second host compound shown in Table1 below were respectively used as hosts of the light-emitting layer.

The driving voltage, luminous efficiency, and light-emitting color at aluminance of 1,000 nit, and the time taken to reduce from the initialluminance of 100% to a luminance of 95% in a luminance of 5,500 nit(T95) of the OLEDs produced in Device Examples 1-1 to 1-3 andComparative Examples 1-1 to 1-4, are shown in Table 1 below.

TABLE 1 First Host Second Host Driving Voltage [V] Luminous Efficiency[cd/A] Light-Emitting Color Lifetime (T95) [hr] Device Example 1-1 H1-11H2-3 2.9 32.0 Red 640 Device Example 1-2 H1-11 H2-10 3.1 32.5 Red 524Device Example 1-3 H1-11 H2-2 3.0 33.8 Red 394 Comparative Example 1-1 -H2-3 3.5 24.7 Red 57.5 Comparative Example 1-2 - H2-10 4.0 25.6 Red 45.9Comparative Example 1-3 - H2-2 3.3 28.4 Red 52.6 Comparative Example 1-4H1-11 A-1 3.0 32.3 Red 321

From Table 1 above, it can be confirmed that the organicelectroluminescent devices comprising a specific combination ofcompounds of the present disclosure as host materials have significantlyreduced driving voltage and remarkably improved luminous efficiency andlifetime properties as compared with conventional organicelectroluminescent devices.

Device Examples 2-1 to 2-3: Producing an OLED According to the PresentDisclosure

An OLED was produced in the same manner as in Device Example 1-1, exceptthat a light-emitting layer was formed as follows: The compound shown inTable 2 below as a host was introduced into a cell of the vacuum vapordeposition apparatus, and compound D-39 was introduced into another cellof the vacuum vapor deposition apparatus as a dopant. The two materialswere evaporated at different rates to be deposited in a doping amount ofthe dopant of 3 wt% based on the total amount of the host and the dopantto form a light-emitting layer having a thickness of 40 nm on the secondhole transport layer.

Comparative Example 2-1: Producing an OLED Comprising a ComparativeCompound

An OLED was produced in the same manner as in Device Example 2-1, exceptthat compound A-1 shown in Table 3 below was used as a host of thelight-emitting layer.

The time taken to reduce from the initial luminance of 100% to aluminance of 95% in a luminance of 5,500 nit (T95) of the OLEDs producedin Device Examples 2-1 to 2-3 and Comparative Example 2-1, are shown inTable 2 below.

TABLE 2 Host Lifetime (T95) [hr] Device Example 2-1 H2-3 57.5 DeviceExample 2-2 H2-10 45.9 Device Example 2-3 H2-2 52.6 Comparative Example2-1 A-1 27.3

From Table 2 above, it can be confirmed that the organicelectroluminescent devices comprising the compounds according to thepresent disclosure as host materials have longer lifetime properties ascompared with conventional organic electroluminescent devices.

The compounds used in the Device Examples and the Comparative Examplesare shown in Table 3 below.

TABLE 3 Hole Injection Layer / Hole Transport Layer

Light-Emitting Layer

Electron transport Layer / Electron Injection Layer

1. An organic electroluminescent compound represented by the followingformula 3:

wherein, Ar₂₁ and Ar₂₂, each independently, represent a phenylunsubstituted or substituted with deuterium(s), a biphenyl unsubstitutedor substituted with deuterium(s), a terphenyl unsubstituted orsubstituted with deuterium(s), or a naphthyl unsubstituted orsubstituted with deuterium(s); L₂₁ represents a naphthyleneunsubstituted or substituted with deuterium(s), or a biphenyleneunsubstituted or substituted with deuterium(s); R₁, R₄, R₅, and R₈, eachindependently, represent hydrogen, deuterium, a phenyl unsubstituted orsubstituted with deuterium(s), a biphenyl unsubstituted or substitutedwith deuterium(s), a terphenyl unsubstituted or substituted withdeuterium(s), or a naphthyl unsubstituted or substituted withdeuterium(s); and R₂, R₃, R₆, and R₇, each independently, representhydrogen or deuterium; with the proviso that if both Ar₂₁ and Ar₂₂represent phenyl, at least one of R₁, R₄, R₅, and R₈ is not hydrogen ordeuterium.
 2. The organic electroluminescent compound according to claim1, wherein the compound represented by formula 3 is at least oneselected from the following compounds:

.
 3. An organic electroluminescent device comprising the organicelectroluminescent compound according to claim 1.